Primary cell



May 20, 1952 J. J. COLEMAN ET AL PRIMARY CELL Filed Nov. 20, 1948 13 M PERCHLORATE IN METHYL ACETATE CARBON 15 Mn 02 J4 Patented May 20, 1952 PRIMARY CELL Joseph J. Coleman and Demetrios V. Louzos, Freeport, Ill., assignors, by mesne assignments, to Burgess Battery Company, Freeport, 11]., a

corporation of Delaware Application November 20, 1948, Serial No. 61,248

3 Claims.

This invention relates to improvements in primary cells adapted for the delivery of electrical current, and particularly to an improved primary cell having a non-aqueous electrolyte.

Heretofore, current producing primary cells have employed aqueous electrolytes. The principal reason for this is that water readily ionizes the electrolyte compound and such ionization promotes electrolytic action and conductivity. It has been the belief heretofore that an aqueous electrolyte is necessary in order to provide the ionization required for the satisfactory production of current output.

The use of an aqueous electrolyte, however, has the disadvantage that it tends to attack the negative electrode While the cell is not in operation, with the result that the cell undergoes persistent deterioration and exhaustion unless the mentioned tendency is successfully resisted. The avoidance of excessive deterioration and exhaustion from this cause has been oneof the chief problems confronting the primary battery industry. The tendency is more pronounced with the more highly electronegative metals, such as magnesium, and the use of such metals has been generally avoided for this reason. The latter are naturally more desirable because they impart to the cell a higher voltage and the ability to deliver a greater amount of electrical energy but, nevertheless, little use has been made of them in the past because they are more susceptible to attack by the aqueous electrolyte.

In accordance with the present invention, it has been found that primary cells having satisfactory current delivering properties can be made with an electrolyte containing a nonaqueous solvent, that is, a substantially waterfree organic solvent. It has been found that certain non-aqueous solvents dissolve electrolyte salts and otherwise function in a manner such as to provide suitable electrolytic action and satisfactory energy delivery performance. In addition, such electrolytes containing non-aqueous solvents exhibit markedly less attack upon the negative electrode than do Water and the aqueous electrolytes employed heretofore.

It is the object of the invention to provide an improved primary cell employing a non-aqueous solvent in the electrolyte in which cell the negative electrode suffers only slight attack by the electrolyte and does not undergo objectionable deterioration and exhaustion when the cell is not in operation.

It is a further object of the invention to make it possible to use a more highly electronegative metal such as magnesium for the negative electrode, thus providing a cell having a higher vo1tage and reducing the number of cells required in a battery of predetermined voltage, and, in general, providing a battery capable of delivering a high output of electrical energy for its size. Another advantage obtained from'the use of magnesium is that it is one of the more abundant and readily available metals.

Other objects and advantages will become apparent as the following description progresses. which is to be taken in conjunction with the accompanying drawing, in which the single figure is a sectional elevation of a primary cell in accordance with the present invention.

The cell comprises a container H] which is generally rectangular in shape, but may be of any desired shape, and is open at the top. The container is composed of a non-conductive material which is resistant to moisture and the electrolyte of the cell, such as rubber hydrochloride, phenol formaldehyde resin, or the like.

Adjacent to the interior surface of a wall of container I0 is the metal negative electrode [2 which is in the form of a fiat plate having a height somewhat less than that of the container l0. Adjacent to the negative electrode is a layer of bibulous non-conductive material l3, such as blotting paper. The bibulous layer l3 absorbs the liquid electrolyte of the cell. Adjacent 'to the bibulous layer I3 is a body of oxidizing material M which may be a compacted liquid absorbent mass of finely divided particles of a mixture of conductive material, such as graphite, carbon black or other form of carbon, and an oxidizing agent which serves as a depolarizer for the cell. Said oxidizing agent will be described more fully hereinafter. The proportions of oxidizing agent and conductive material are not critical, it being necessary only to provide sufficient of each to afford the desired conductivity and oxidizing activity. The oxidizing body [4 absorbs the electrolyte, whereby the electrolyte is present in both the body It and the bibulous layer I3.

Embedded in the oxidizing body I 4 and in conductive contact therewith is the positive electrode l5 of the cell, which may be, composed of an inert conductive substance and may be in any desired form. In the specific cell shown, it is composed of carbon and is in the form of a cylindrical rod having its upper end portion projecting above the oxidizing body I4. The said projecting end has a metal cap 16 fitting frictionally thereover, said cap serving as one terminal of the cell. The negative electrode 12 has a conductor I! connected thereto and servis sealed by pouring into the upper portion of 1 the container I and upon the sheet IS a molten sealing composition, such as wax or pitch, which solidifies upon cooling to form the seal closure Ill. The terminals 18 and I1 project above the sheet [8 and the seal I9 and are adapted for connection to an external circuit.

A liquid electrolyte is introduced into the container l0 and is absorbed and retained by the bibulous layer 13 and the oxidizing body l4 and is in conductive contact with the negative electrode l2 and the oxidizing body 14. The electrolyte of the cell is a solution comprising a solvent component which is a non-aqueous liquid and a solute component which is a compound which renders the solution conductive and when in the solution is electrolytically reactive and spontaneously unreactive toward the negative electrode.

In accordance with the present invention, the solvent which may be employed is methyl acetate, CHsCOOCI-Iz. This compound is a liquid at ordinary temperatures and by itself is inert toward the electrodes and the oxidizing agent, i. e., does not appreciably attack or corrode said elements.

Magnesium is employed for the negative electrode l2. Magnesium has the advantages that it is readily available, stable under most condi tions, and produces a relatively high cell voltage.

For the positive electrode [5, a conductive material is chosen which is substantially inert toward the electrolyte, both in the presence and the absence of the electrolytic action of the cell. Carbon is suitable and where silver chloride is used as the oxidizing agent as described hereinafter, silver may be used. In the specific cell illustrated, the electrode I is a compressed body of carbon similar to that commonly used in dry cells of the LeClanche type.

For the reactive electrolyte compound, magnesium perchlorate is used. This compound is soluble in the organic solvent and forms therewith an electrolytically conductive solution. Also, when in solution in the solvent it is electrolytically reactive toward the material of the negative electrode, but .is spontaneously unreactive toward said electrode, i. e., it is reactive toward the negative electrode when the cell electrodes are connected together through an external circuit and the cell is operative, and unreactive when the electrodes are not connected together and the cell is inoperative. Also, it does not cause the plating of metal upon the negative electrode. The amount of reactive compound is not critical, it being only necessary to supply sufficient thereof to provide the de sired reactivity and conductivity. During operation of the cell, the electrolyte enter into reaction with the negative electrode.

At ordinary temperature, magnesium perchlorate exists as the anhydrous compound,

Mg(C1D4)'2 and also in the form of various hydrates includ- 4 ing the dihydrate, Mg(ClO4) 2.21120, the trihydrate, Mg(ClO4)2.3H2O, the tetrahydrate,

Mg (C104) 2.4H2O

and the hexahydrate, Mg (0100261120 (J. A. C. S. vol. 54, pp. 3513-3523 (1932)). These hydrates, as well as the anhydrous compound, are suitable in the non-aqueous system of the present invention. When the solid hydrate goes into solution in the organic solvent, it continues to exhibit hydrating power, that is, the power to bind water, and the water of hydration remains bound thereto and the organic solvent remains free of water. In some instances a small amount of the water may become dissociated from the compound and exist in freedom in the solvent. Such water will then react with the negative electrode and cause a slight corrosion of the latter. Such water is quickly consumed, however, and does not do objectionable damage, and the solvent again assumes its non-aqueous character. In the same way, the invention contemplates that a small amount of water may be present initially in the electrolyte. This water is quickly consumed in reacting with the negative electrode and the solvent then assumes its non-aqueous character. The solution of th reactive electrolyte compound in the solvent forms the electrolyte of the cell.

For the oxidizing agent which is included in the oxidizing body l4, manganese dioxide and silver chloride have been found to be suitable in accordance with the present invention. The oxidizing agent is one of the factors which determines the potential of the positive electrode.

The solution which has been described heretofore and which is held by the oxidizing body I4 and the absorbent layer 13 forms the electrolyte for the cell, providing electrolytic conductivity between the electrodes ['2 and I5 and entering readily into electrolytic reaction with the negative electrode 12 and the oxidizing body It, whereby the cell has strong current delivering powers.

A specific example of a satisfactory cell in accordance with the invention is one having the mechanical construction described heretofore and elements of the composition which will be described. The negative electrode is composed of magnesium and the positive electrode is composed of carbon. The solvent is methyl acetate and the .reactive electrolyte compound is magnesium perchlorate, which is present in an amount suificient to form a saturated solution at 20 C. Such an electrolyte provides satisfactory reactivity and conductivity. The oxidizing body 14 is a mixture, the solid components of which comprise approximately 90% by weight of finely divided manganese dioxide and approximately 10% of thermal acetylene black. The separating member [3 is composed of blotting paper. Such a cell has an open circuit voltage of 1.84 volts, and is adapted to deliver current of substantial value.

This application is a continuation-in-part of our application Serial No. 713,944, filed December 4, 1946, now abandoned. Primary cells of a character generally similar to that described herein and employing various organic solvents in the electrolyte in contact with said electrodes comprising a substantially water-free methyl acetate solvent containing magnesium perchlorate dissolved therein, and an oxidizing agent exposed to said electrolyte and in conductive contact with said positive electrode.

2. A primary cell comprising positive and negative electrodes composed of carbon and magnesium respectively, an electrolyte in contact with said electrodes comprising a substantially waterfree methyl acetate solvent having magnesium perchlorate dissolved therein, and an oxidizing agent composed of manganese dioxide exposed to said electrolyte and in conductive contact with said positive electrode.

3. A primary cell comprising a positive electrode and a magnesium negative electrode, and an electrolyte in contact with said electrodes comprising a substantially water-free methyl acetate solvent containing magnesium perchlorate dissolved therein.

JOSEPH J. COLEMAN. DEMETRIOS V. LOUZOS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 393,573 Paget Nov. 27, 1888 1,920,151 Ruben July 25, 1933 2,428,850 Lawson Oct. 14, 1947 FOREIGN PATENTS Number Country Date 391,468 France Aug. 31, 1908 

3. A PRIMARY CELL COMPRISING A POSITIVE ELECTRODE AND A MAGNESIUM NEGATIVE ELECTRODE, AND AN ELECTROLYTE IN CONTACT WITH SAID ELECTRODES COMPRISING A SUBSTANTIALLY WATER-FREE METHYL ACETATE SOLVENT CONTAINING MAGNESIUM PERCHLORATE DISSOLVED THEREIN. 